Stabilized low-concentration metsulfuron-methyl liquid composition

ABSTRACT

Disclosed are a single liquid-phase herbicide composition comprising by weight of the composition: (a) from 0.1 to 1% of metsulfuron-methyl; (b) from 1 to 20% of thifensulfuron-methyl; (c) from 30 to 93% of one or more fatty acid esters of C1-C4 alkanols; and (d) from 5 to 25% of one or more surfactants having an emulsifier property, and a process for preparing the composition.

FIELD OF THE INVENTION

This invention provides a stable liquid herbicide composition comprisingmetsulfuron-methyl not exceeding 1% of the composition by weight, whichaccommodates including higher concentrations of less active herbicidesin the composition.

BACKGROUND OF THE INVENTION

Since its first marketing approval in 1984, metsulfuron-methyl hasbecome one of the most commercially important herbicides for control ofa wide range of grass and broad-leaved weeds in crops including wheat,barley, oats and triticale through post-emergence application (see ThePesticide Manual, Sixteenth Edition, C. MacBean ed., British CropProtection Council, Hampshire, UK, 2012, pp. 782-3). Like othersulfonylurea herbicides, the mode of action of metsulfuron-methylinvolves inhibition of the enzyme acetolactate synthase (ALS) found inplants but not animals, and therefore metsulfuron-methyl provides avalued combination of excellent efficacy against weeds with low userates and very low toxicity to animals.

Since its introduction, metsulfuron-methyl has typically been formulatedin herbicide products as solid compositions, such as granules,particularly water-dispersible or water-soluble granules, and tablets.Not only can granules and tablets be readily dispensed, butmetsulfuron-methyl generally has excellent storage stability in solidcompositions.

Although metsulfuron-methyl controls a wide range of weeds, combinationwith other active ingredients, particularly other herbicides, can bedesirable to provide a broader spectrum of protection or for resistancemanagement. Solid compositions are suitable for metsulfuron-methyl incombination with other high-melting active ingredients, but includingactive ingredients that are liquids or low-melting in a solidcomposition can be difficult.

Concentrated liquid compositions can readily include not only activeingredients that are liquids or low-melting but also high-melting activeingredients such as sulfonylurea herbicides, which generally are mostlypresent in the form of solid particles dispersed in a liquid carrier.Such liquid concentrate formulations can be easily measured and poured,and when diluted with water typically give easily sprayed aqueoussolutions, emulsions or dispersions.

However, compared to solid formulations, liquid formulations ofsulfonylureas are more prone to certain problems. When dissolved ordispersed in a liquid carrier, even a carrier comprising a nonaqueoussolvent, sulfonylurea herbicides may be susceptible to decomposition.Also, crystal growth can occur during storage of concentrated liquidformulations in which active ingredients are dissolved or dispersed, andsuspended active ingredients are prone to settling out, so thatobtaining stable liquid formulations is challenging.

Because of its high herbicidal activity, metsulfuron-methyl is typicallyapplied at very low rates, e.g., 4-8 g/ha. Accordingly when combinedwith much higher use rate herbicides in a concentrated formulatedcomposition, metsulfuron-methyl must be in low concentration toaccommodate a sufficiently high concentration of higher use rateherbicides in the composition. However, it has now been found thatalthough metsulfuron-methyl is sufficiently stable at high concentrationin liquid carriers comprising one or more fatty acid esters of C₁-C₄alkanols in the presence of one or more surfactants having an emulsifierproperty, at concentrations of 1% or less, metsulfuron-methyl issusceptible to undergoing decomposition to a commercially undesirableextent during storage of the composition.

Remarkably, as described herein, a surprising means of stabilization oflow concentrations of metsulfuron-methyl in such a liquid compositionhas now been discovered, thus providing a new stabilized liquidcomposition for dilution with water and application to undesirablevegetation to be controlled.

SUMMARY OF THE INVENTION

This invention is directed to a single liquid-phase herbicidecomposition comprising by weight of the composition:

(a) from 0.1 to 1% of metsulfuron-methyl;

(b) from 1 to 20% of thifensulfuron-methyl;

(c) from 30 to 93% of one or more fatty acid esters of C₁-C₄ alkanols;and

(d) from 5 to 25% of one or more surfactants having an emulsifierproperty.

This invention also relates to a process for preparing said composition,the process comprising milling components (a) and (b) together in aliquid carrier comprising components (c) and (d).

DETAILED DESCRIPTION OF THE INVENTION

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having,” “contains”, “containing,” “characterizedby” or any other variation thereof, are intended to cover anon-exclusive inclusion, subject to any limitation explicitly indicated.For example, a composition, mixture, process, or method that comprises alist of elements is not necessarily limited to only those elements butmay include other elements not expressly listed or inherent to suchcomposition, mixture, process, or method.

The transitional phrase “consisting of” excludes any element, step, oringredient not specified. If in the claim, such would close the claim tothe inclusion of materials other than those recited except forimpurities ordinarily associated therewith. When the phrase “consistingof” appears in a clause of the body of a claim, rather than immediatelyfollowing the preamble, it limits only the element set forth in thatclause; other elements are not excluded from the claim as a whole.

The transitional phrase “consisting essentially of” is used to define acomposition or method that includes materials, steps, features,components, or elements, in addition to those literally disclosed,provided that these additional materials, steps, features, components,or elements do not materially affect the basic and novelcharacteristic(s) of the claimed invention. The term “consistingessentially of” occupies a middle ground between “comprising” and“consisting of”.

Where applicants have defined an invention or a portion thereof with anopen-ended term such as “comprising,” it should be readily understoodthat (unless otherwise stated) the description should be interpreted toalso describe such an invention using the terms “consisting essentiallyof” or “consisting of ”

Further, unless expressly stated to the contrary, “or” refers to aninclusive or and not to an exclusive or. For example, a condition A or Bis satisfied by any one of the following: A is true (or present) and Bis false (or not present), A is false (or not present) and B is true (orpresent), and both A and B are true (or present).

Also, the indefinite articles “a” and “an” preceding an element orcomponent of the invention are intended to be nonrestrictive regardingthe number of instances (i.e. occurrences) of the element or component.Therefore “a” or “an” should be read to include one or at least one, andthe singular word form of the element or component also includes theplural unless the number is obviously meant to be singular.

The term “single liquid-phase composition” and derivative terms such as“single liquid-phase herbicide composition” refer to compositionsconsisting of a single liquid phase. The term “single liquid-phasecomposition” therefore excludes compositions comprising a plurality ofliquid phases such as emulsions. The term “single liquid-phasecomposition” does not exclude compositions comprising one or more solidphases in addition to the single liquid phase, such as suspensions anddispersions of solid particles.

As used in the present disclosure and claims, the term “fatty acid”refers to a monocarboxylic acid having a hydrocarbon chain containing 3to 23, more particularly 3 to 21 carbon atoms. The hydrocarbon chain maybe branched and may be unsaturated (e.g., contain one or morecarbon-carbon double bonds).

As used in the present disclosure and claims, the term “polymerizedfatty acid” generally refers to a polymer derived from fatty acidmonomers. Polymerized fatty acids include, for example, polymers formedby esterification of the carboxylic acid and hydroxy functions ofhydroxy fatty acids such as ricinoleic acid or hydrogenated ricinoleicacid (12-hydroxyoctadecanoic acid). Polymerized fatty acids include bothhomopolymers, formed, for example, from just one fatty acid monomer,e.g., 12-hydroxyoctadecanoic acid, and copolymers formed from two ormore fatty acid monomers, e.g., both ricinoleic acid and12-hydroxyoctadecanoic acid. Furthermore the term “polymerized fattyacid” also includes fatty acid polymers having fatty acid unitsterminating polymerization, for example a non-hydroxy fatty acid in apolymer of hydroxy fatty acids (e.g., 12-hydroxyoctadecanoic acidhomopolymer, octadecanoate). These can be considered fatty acid estersof fatty acid polymers.

Particle size (or size of particles) as referred to herein relates tothe volume moment mean, also known as the volume mean and the DeBroucker mean. The principles of particle size analysis are well knownto those skilled in the art; for a technical paper providing a summary,see A. Rawle, “Basic Principles of Particle Size Analysis” (documentMRK034 published by Malvern Instruments Ltd., Malvern, Worcestershire,UK). Volume distributions of particles in liquid suspensions can beconveniently measured by such techniques as Low Angle Laser LightScattering (also known as LALLS and Laser Diffraction), which relies onthe fact that diffraction angle is inversely proportional to particlesize. Commercially available instruments suitable for analyzing usingLALLS the volume distributions of particles in liquid suspensionsinclude the Mastersizer 2000 (Malvern Instruments, Worcestershire, UK).The Mastersizer can determine D10, D50 and D90 percentiles, which aresize values corresponding to the cumulative distribution at 10%, 50% and90%. Thus, the D10 value represents a size value below which 10% of thecumulative distribution is present, and similarly D90 represents a sizevalue below which 90% of the cumulative distribution occurs. The D50value therefore, corresponds to the median diameter and divides thedistribution exactly in half.

Embodiments of the present invention as described in the Summary of theInvention include those described below.

Embodiment A1. The composition according to the Summary of the Inventionwherein component (a) is at least 0.2% of the composition by weight.

Embodiment A2. The composition of Embodiment A1 wherein component (a) isat least 0.3% of the composition by weight.

Embodiment A3. The composition of Embodiment A2 wherein component (a) isat least 0.4% of the composition by weight.

Embodiment A4. The composition according to the Summary of the Inventionor any one of Embodiments A1 through A3 wherein component (a) is notmore than 0.9% of the composition by weight.

Embodiment A5. The composition of Embodiment A4 wherein component (a) isnot more than 0.8% of the composition by weight.

Embodiment A6. The composition of Embodiment A5 wherein component (a) isnot more than 0.7% of the composition by weight.

Embodiment A7. The composition of Embodiment A6 wherein component (a) isnot more than 0.6% of the composition by weight.

Embodiment B1. The composition according to the Summary of the Inventionor any one of Embodiments A1 through A7 wherein component (b) is atleast 2% of the composition by weight.

Embodiment B2. The composition according to the Summary of the Inventionor any one of Embodiments A1 through B1 wherein component (b) is notmore than 10% of the composition by weight.

Embodiment B3. The composition of Embodiment B2 wherein component (b) isnot more than 8% of the composition by weight.

Embodiment B4. The composition of Embodiment B3 wherein component (b) isnot more than 6% of the composition by weight.

Embodiment B5. The composition of Embodiment B4 wherein component (b) isnot more than 5% of the composition by weight.

Embodiment B6. The composition of Embodiment B5 wherein component (b) isnot more than 4% of the composition by weight.

Embodiment C1. The composition according to the Summary of the Inventionor any one of Embodiments A1 through B6 wherein component (c) is atleast 35% of the composition by weight.

Embodiment C2. The composition of Embodiment C1 wherein component (c) isat least 40% of the composition by weight.

Embodiment C3. The composition according to the Summary of the Inventionor any one of Embodiments A1 through C2 wherein component (c) is notmore than 90% of the composition by weight.

Embodiment C4. The composition of Embodiment C3 wherein component (c) isnot more than 80% of the composition by weight.

Embodiment C5. The composition of Embodiment C4 wherein component (c) isnot more than 65% of the composition by weight.

Embodiment C6. The composition of Embodiment C5 wherein component (c) isnot more than 60% of the composition by weight.

Embodiment C7. The composition of Embodiment C6 wherein component (c) isnot more than 55% of the composition by weight.

Embodiment C8. The composition according to the Summary of the Inventionor any one of Embodiments A1 through C7 wherein component (c) comprisesone or more C₁-C₄ alkyl esters of fatty acids containing 8 to 22 carbonatoms.

Embodiment C9. The composition of Embodiment C8 wherein at least 80% byweight of component (c) consists of esters of fatty acids containing 8to 22 carbon atoms.

Embodiment C10. The composition of Embodiment C9 wherein at least 90% byweight of component (c) consists of esters of fatty acids containing 8to 22 carbon atoms.

Embodiment C11. The composition according to the Summary of theInvention or any one of Embodiments A1 through C10 wherein component (c)comprises methyl esters of one or more fatty acids.

Embodiment C12. The composition according to the Summary of theInvention or any one of Embodiments A1 through C11 wherein component (c)comprises one or more methylated vegetable (e.g., seed) oils.

Embodiment C13. The composition of Embodiment C12 wherein component (c)comprises one or more methylated seed oils of sunflower, soybean,rapeseed, cotton, linseed, oil palm or coconut.

Embodiment C14. The composition of Embodiment C13 wherein component (c)comprises one or more methylated seed oils of soybean, rapeseed orcoconut.

Embodiment C15. The composition of Embodiment C14 wherein component (c)comprises methylated soybean oil.

Embodiment C16. The composition of Embodiment C14 wherein component (c)comprises methylated coconut oil.

Embodiment C17. The composition of Embodiment C14 wherein component (c)comprises a mixture of methylated soybean oil and methylated coconutoil.

Embodiment C18. The composition according to the Summary of theInvention or any one of Embodiments A1 through C17 wherein component (c)in its isolated form (i.e. not part of the composition) has a cloudpoint (according to ASTM Standard Method D2500 (1994)) less than 15° C.

Embodiment C19. The composition according to the Summary of theInvention or any one of Embodiments A1 through C18 at a temperature ofat least 15° C.

Embodiment C20. The composition according to the Summary of theInvention or any one of Embodiments A1 through C19 having a liquidcarrier formed by (i.e. comprising) component (c).

Embodiment Dl. The composition according to the Summary of the Inventionor any one of Embodiments A1 through C20 wherein component (d) is atleast 10% of the composition by weight.

Embodiment D2. The composition according to the Summary of the Inventionor any one of Embodiments A1 through D1 wherein component (d) is notmore than 20% of the composition by weight.

Embodiment D3. The composition according to the Summary of the Inventionor any one of Embodiments A1 through D2 wherein component (d) comprisesat least one surfactant selected from alkylbenzenesulfonates,alkylnaphthalenesulfonates, ethoxylated triglycerides, ethoxylatedtri-styryl phenols, ethoxylated aliphatic alcohols, ethoxylated sorbitanmono- and tri-esters, ethoxylated sorbitol hexa-esters andpolyoxyethylene-polyoxypropylene block copolymers, including mixturesthereof.

Embodiment D4. The composition according to the Summary of the Inventionor any one of Embodiments A1 through D3 wherein component (d) comprisesat least one surfactant selected from anionic surfactants and at leastone surfactant selected from nonionic surfactants.

Embodiment D5. The composition according to the Summary of the Inventionor any one of Embodiments A1 through D4 wherein component (d) isdissolved in component (c) forming the liquid carrier of thecomposition.

Embodiment E1. The composition according to the Summary of the Inventionor any one of Embodiments A1 through D5 further comprising (e) up to 40%of one or more biologically active agents other than metsulfuron-methyland thifensulfuron-methyl.

Embodiment E2. The composition of Embodiment E1 wherein component (e) isat least 0.1% of the composition by weight.

Embodiment E3. The composition of Embodiment E2 wherein component (e) isat least 1% of the composition by weight.

Embodiment E4. The composition of Embodiment E3 wherein component (e) isat least 5% of the composition by weight.

Embodiment E5. The composition of Embodiment E4 wherein component (e) isat least 10% of the composition by weight. Embodiment E6. Thecomposition of Embodiment E5 wherein component (e) is at least 15% ofthe composition by weight.

Embodiment E7. The composition of Embodiment E6 wherein component (e) isat least 20% of the composition by weight.

Embodiment E8. The composition according to the Summary of the Inventionor any one of Embodiments A1 through E7 wherein component (e) is notmore than 35% of the composition by weight.

Embodiment E9. The composition of Embodiment E8 wherein component (e) isnot more than 30% of the composition by weight.

Embodiment E10. The composition according to the Summary of theInvention or any one of Embodiments A1 through E9 wherein component (e)comprises one or more herbicides or herbicide safeners.

Embodiment E11. The composition according to the Summary of theInvention or any one of Embodiments A1 through E10 wherein component (e)comprises one or more herbicides.

Embodiment E12. The composition according to the Summary of theInvention or any one of Embodiments A1 through E11 wherein component (e)comprises one or more fluroxypyr esters.

Embodiment E13. The composition according to the Summary of theInvention or any one of Embodiments A1 through E12 wherein thecomposition comprises at least 5% by weight of one or more fluroxypyresters.

Embodiment E14. The composition of Embodiment E13 wherein thecomposition comprises at least 15% by weight of one or more fluroxypyresters.

Embodiment E15. The composition according to the Summary of theInvention or any one of Embodiments A1 through E14 wherein thecomposition comprises not more than 40% by weight of one or morefluroxypyr esters.

Embodiment E16. The composition of Embodiment E15 wherein thecomposition comprises not more than 25% by weight of one of morefluroxypyr esters.

Embodiment E17. The composition according to the Summary of theInvention or any one of Embodiments A1 through E11 wherein component (e)comprises one or more bromoxynil esters.

Embodiment E18. The composition of Embodiment E17 wherein component (d)comprises one or more C₆-C₁₀ alkanoate esters of bromoxynil.

Embodiment E19. The composition according to the Summary of theInvention or any one of Embodiments A1 through E18 wherein thecomposition comprises at least 5% by weight of one or more bromoxynilesters.

Embodiment E20. The composition of Embodiment E19 wherein thecomposition comprises at least 25% by weight of one or more bromoxynilesters.

Embodiment E21. The composition according to the Summary of theInvention or any one of Embodiments A1 through E20 wherein thecomposition comprises not more than 40% by weight of one or morebromoxynil esters.

Embodiment E22. The composition of Embodiment E21 wherein thecomposition comprises not more than 35% by weight of one or morebromoxynil esters.

Embodiment E23. The composition according to the Summary of theInvention or any one of Embodiments A1 through E22 wherein component (e)is dissolved in component (c) forming the liquid carrier of thecomposition.

Embodiment F1. The composition according to the Summary of the Inventionor any one of Embodiments A1 through E23 further comprising (0 up to 63%of one or more additional formulating ingredients.

Embodiment F2. The composition of Embodiment F1 wherein component (f) isat least 0.1% of the composition by weight.

Embodiment F3. The composition of Embodiment F2 wherein component (f) isat least 1% of the composition by weight.

Embodiment F4. The composition of Embodiment F3 wherein component (f) isat least 2% of the composition by weight.

Embodiment F5. The composition of Embodiment F4 wherein component (f) isat least 3% of the composition by weight.

Embodiment F6. The composition of any one of Embodiments F1 through F5wherein component (f) is not more than 60% of the composition by weight.

Embodiment F7. The composition of Embodiment F6 wherein component (f) isnot more than 50% of the composition by weight.

Embodiment F8. The composition of Embodiment F7 wherein component (f) isnot more than 40% of the composition by weight.

Embodiment F9. The composition of Embodiment F8 wherein component (f) isnot more than 30% of the composition by weight.

Embodiment F10. The composition of Embodiment F9 wherein component (f)is not more than 20% of the composition by weight.

Embodiment F11. The composition of Embodiment F10 wherein component (f)is not more than 15% of the composition by weight.

Embodiment F12. The composition of Embodiment F11 wherein component (f)is not more than 10% of the composition by weight.

Embodiment F13. The composition of any one of Embodiments F1 through F12wherein component (f) comprises at least one constituent selected from(1) surfactants not having a significant emulsifier property, and (2)thickening agents.

Embodiment F14. The composition according to the Summary of theInvention or any one of Embodiments A1 through F13 wherein thecomposition comprises (i.e. as a constituent in component (f) one ormore surfactants having a dispersant property but not (having) anemulsifier property.

Embodiment F15. The composition of Embodiment F14 wherein thecomposition comprises by weight up to 10% of the surfactant constituent(i.e. one or more surfactants) having a dispersant property but not anemulsifier property.

Embodiment F16. The composition of Embodiment F15 wherein thecomposition comprises by weight up to 5% of the surfactant constituent(i.e., one or more surfactants) having a dispersant property but not anemulsifier property.

Embodiment F17. The composition of any one of Embodiments F14 throughF16 wherein the composition comprises by weight at least 0.1% of thesurfactant constituent having a dispersant property but not anemulsifier property.

Embodiment F18. The composition of Embodiment F17 wherein thecomposition comprises by weight at least 1% of the surfactantconstituent having a dispersant property but not an emulsifier property.

Embodiment F19. The composition of Embodiment F18 wherein thecomposition comprises by weight at least 2% of the surfactantconstituent having a dispersant property but not an emulsifier property.

Embodiment F20. The composition of any one of Embodiments F14 throughF19 wherein the surfactant constituent having a dispersant property butnot an emulsifier property comprises one or more polymerized fattyacids.

Embodiment F21. The composition of Embodiment F20 wherein the surfactantconstituent having a dispersant property but not an emulsifier propertycomprises 12-hydroxyoctadecanoic acid homopolymer (CAS Number27924-99-8), ricinoleic acid homopolymer (CAS Number 27925-02-6), or afatty acid ester thereof.

Embodiment F22. The composition of Embodiment F21 wherein the surfactantconstituent having a dispersant property but not an emulsifier propertycomprises 12-hydroxyoctadecanoic acid homopolymer, octadecanoate (CASNumber 58128-22-6).

Embodiment F23. The composition according to the Summary of theInvention or any one of Embodiments A1 through F22 wherein thecomposition or the surfactant constituent having a dispersant propertybut not an emulsifier property comprises one or more polymerized fattyacids in an amount of 2 to 5% of the composition by weight.

Embodiment F24. The composition according to the Summary of theInvention or any one of Embodiments A1 through F23 wherein thecomposition comprises (i.e. as a constituent in component (f) one ormore thickening agents.

Embodiment F25. The composition of Embodiment F24 wherein thecomposition comprises by weight up to 5% of the thickening agentconstituent (i.e. one or more thickening agents).

Embodiment F26. The composition of Embodiment F25 wherein thecomposition comprises by weight not more than 4% of the thickening agentconstituent.

Embodiment F27. The composition of Embodiment F26 wherein thecomposition comprises by weight not more than 3% of the thickening agentconstituent.

Embodiment F28. The composition of Embodiment F27 wherein thecomposition comprises by weight not more than 2% of the thickening agentconstituent.

Embodiment F29. The composition of any one of Embodiments F24 throughF28 wherein the composition comprises by weight at least 0.1% of thethickening agent constituent.

Embodiment F30. The composition of Embodiment F29 wherein thecomposition comprises by weight at least 0.5% of the thickening agentconstituent.

Embodiment F31. The composition of any one of Embodiments F24 throughF30 wherein the thickening agent constituent comprises one or moresilicas or silicates.

Embodiment F32. The composition of Embodiment F31 wherein the thickeningagent constituent comprises one or more organically modified silicas orsilicates.

Embodiment F33. The composition of any one of Embodiments F24 throughF32 wherein the thickening agent constituent comprises one or moreorganically modified clays.

Embodiment F34. The composition according to the Summary of theInvention or any one of Embodiments A1 through F33 comprising by weightfrom 0.5 to 5% of one or more organically modified clays.

Embodiment G1. The composition according to the Summary of the Inventionor any one of Embodiments A1 through F34 not containing more than 10%water by weight.

Embodiment G2. The composition according to Embodiment Gl not containingmore than 5% water by weight.

Embodiment G3. The composition according to Embodiment G2 not containingmore than 3% water by weight.

Embodiment G4. The composition according to Embodiment G3 not containingmore than 2% water by weight.

Embodiment G5. The composition according to Embodiment G4 not containingmore than 1% water by weight.

Embodiments of this invention, including Embodiments A1 through G5 aboveas well as any other embodiments described herein, can be combined inany manner. In addition, embodiments of this invention, includingEmbodiments A1 through G5 above as well as any other embodimentsdescribed herein, and any combination thereof, pertain to not only thecomposition but also to processes for preparation of the composition andintermediate mixtures and compositions.

As described in the Summary of the Invention, this invention is directedto a single liquid-phase herbicide composition comprising by weight ofthe composition (a) from 0.1 to 1% of metsulfuron-methyl; (b) from 1 to20% of thifensulfuron-methyl; (c) from 30 to 93% of one or more fattyacid esters of C₁-C₄ alkanols; and (d) from 5 to 25% of one or moresurfactants having an emulsifier property (i.e. an emulsifier). Theliquid carrier of this composition comprises component (c) and providesa continuous liquid medium in which other components are dissolved ordispersed. As will be described further, components (a) and (b), both ofwhich are herbicidal, are mostly suspended as solid particles in thepresent composition, and accordingly the composition can be regarded asa herbicidal oil dispersion formulation, i.e. a suspension of solidparticles of components (a) and (b) dispersed in oily component (c).

The present composition contains as component (a) the chemical compoundmethyl2-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]benzoate,which has the common name metsulfuron-methyl and the molecular structureshown as Formula 1.

Methods for preparation of metsulfuron-methyl are disclosed in U.S.Patent 4,383,113, and this herbicidal active ingredient is furtherdescribed in The Pesticide Manual, Sixteenth Edition, C. MacBean ed.,British Crop Protection Council, Hampshire, UK, 2012, pp. 782-783),which discloses a melting point of 162° C. Metsulfuron-methyl hasrelatively low solubility in solvents of low polarity such as fatty acidesters of C₁-C₄ alkanols, and thus is present mostly as solid particlesin the present composition. Of note is at least 90%, 95%, 98% or 99% ofthe metsulfuron-methyl being in the form of suspended solid rather thandissolved. In the present composition, the metsulfuron-methyl ofcomponent (a) is typically in the free acid form having the molecularstructure depicted as Formula 1, rather than as a salt (e.g., whereinthe sulfonylurea bridge —S(O)₂NHC(═O)N— is deprotonated).

In the present composition, metsulfuron-methyl is included in an amountof 0.1 to 1% by weight. More typically, the amount of metsulfuron-methylis at least 0.2%, or 0.3% or 0.4%, and not more than 0.9%, or 0.8%, or0.7% or 0.6% of the composition by weight. This low concentration ofmetsulfuron-methyl accommodates the inclusion of not only the otherrequired components and other formulating auxiliaries, but also greaterconcentrations of other optional active ingredients, includingherbicides that are typically applied at application rates much greaterthan metsulfuron-methyl. It is also at this low concentration that, inthe absence of a stabilizer, metsulfuron-methyl is found to beinsufficiently stable on storage on contact with the liquid mediumcomprising a fatty acid ester of a C₁-C₄ alkanol in the presence of asurfactant having an emulsifier property.

In this regard, the present composition contains as component (b) thechemical compound methyl3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbony1]amino]-sulfonyl]-2-thiophenecarboxylate,which has the common name thifensulfuron-methyl and the molecularstructure shown as Formula 2.

Methods for preparation of thifensulfuron-methyl are disclosed in U.S.Patent 4,481,029, and this herbicidal active ingredient is furtherdescribed in The Pesticide Manual, Sixteenth Edition, C. MacBean ed.,British Crop Protection Council, Hampshire, UK, 2012, pp. 1109-1110),which discloses a melting point of 176° C. Thifensulfuron-methyl hasrelatively low solubility in solvents of low polarity such as fatty acidesters of C₁-C₄ alkanols, and thus is present mostly as solid particlesin the present composition. Of note is at least 90%, 95%, 98% or 99% ofthe thifensulfuron-methyl being in the form of suspended solid ratherthan dissolved. In the present composition, the thifensulfuron-methyl ofcomponent (b) is typically in the free acid form having the molecularstructure depicted as Formula 2, rather than as a salt (e.g., whereinthe sulfonylurea bridge —S(O)₂NHC(═O)N— is deprotonated).

In the present composition, thifensulfuron-methyl is included ascomponent (b) in an amount of 1 to 20% by weight. More typically, theamount of thifensulfuron-methyl is at least 2%, and not more than 10%,or 8%, or 6%, or 5%, or 4% of the composition by weight. Surprisingly,this concentration of thifensulfuron-methyl in component (b) has nowbeen discovered to remarkably enhance the stability themetsulfuron-methyl of component (a) in the present composition, while atthe same time the thifensulfuron-methyl shows minimal degradation.

Although herbicidal, thifensulfuron-methyl like metsulfuron-methyl isrelatively safe to wheat, barley, oats and triticale crops. Thereforeincluding the concentrations specified for thifensulfuron-methyl incombination with metsulfuron-methyl in the present composition retainsthe utility of the composition for selective control of undesiredvegetation in wheat, barley, oats and triticale crops. Also, becausethifensulfuron-methyl generally degrades more rapidly thanmetsulfuron-methyl in the environment, including thifensulfuron-methylin the present composition does not restrict the rotational cropattributes of the present composition. Furthermore, becausethifensulfuron-methyl is herbicidal, its inclusion in the compositionmay provide an improved spectrum or other benefits for weed control.

The present composition contains as component (c) one or more fatty acidesters of C₁-C₄ alkanols in the amount of 30 to 93% of the compositionby weight. More typically, the amount of component (c) is at least 35%or 40%, and not more than 90%, 80%, 65%, 60% or 55% of the compositionby weight.

Fatty acid esters of C₁-C₄ alkanols are simple esters between thecarboxylic acid functionality of fatty acids and hydroxylicfunctionality of C₁-C₄ alkanols. Fatty acid esters of C₁-C₄ alkanols arenot fatty acid esters of glycerol and thus are not properly regarded asvegetable oils. Instead, as described further below, fatty acid estersof C₁-C₄ alkanols can be synthesized by chemical transformation methodsfrom vegetable oils and C₁-C₄ alkanols.

The C₁-C₄ alkanol-derived portions of the fatty acid esters can beunbranched (i.e. straight-chain) or branched, but are typicallyunbranched. For reasons including favorable physical properties,commercial availability and cost, preferably the fatty acid esters arefatty acids esterified with C₁-C₂ alkanols and more preferably C₁alkanol (i.e. methanol). The fatty acid alkanol esters in a compositionof the present invention can be derived from a mixture of alcohols(e.g., methanol and ethanol).

The fatty acid portions of the fatty acid esters of alkanols consist ofa carbonyl moiety bound to a hydrocarbon chain, which can be unbranchedor branched, but is typically unbranched in natural sources. Thehydrocarbon chain can be saturated or unsaturated; typically thehydrocarbon chain is saturated (i.e. alkyl) or contains 1 or 2(occasionally more) carbon-carbon double bonds (i.e. alkenyl). Fattyacid esters of alkanols formed from fatty acids containing an odd numberof carbon atoms (i.e. even number of carbon atoms in the hydrocarbonchain) are useful in the compositions of the present invention as wellas fatty acid esters of alkanols formed from fatty acids containing aneven number of carbon atoms (i.e. odd number of carbon atoms in thehydrocarbon chain). However, fatty acids obtained from natural sourcestypically contain an even number of carbon atoms, and therefore estersof fatty acids containing an even number of carbon atoms are preferredfor reason of commercial availability and cost.

As already mentioned, fatty acids contain at least 4 carbon atoms andare limited to about 22 (rarely 24) carbon atoms from natural sources.Although alkanol esters of lower fatty acids (e.g., containing as few as4 carbon atoms) are useful for the present compositions, alkanol estersof fatty acids having at least 8, more preferably at least 10, carbonatoms are preferred because of favorable physical properties (e.g., lowvolatility). Alkanol esters of lower fatty acids can be mixed withalkanol esters of higher fatty acids to decrease polarity, watersolubility and volatility. As fatty acids obtained from natural sourcestypically contain 8 to 22 carbon atoms, more typically 10 to 22 carbonatoms, alkanol esters of these fatty acids are preferred for reason ofcommercial availability and cost.

As already mentioned, fatty acid compositions obtained from naturalsources (e.g., seed oils) typically consist of fatty acids having arange of chain lengths and different degrees of unsaturation. Alkanolfatty acid ester compositions (i.e. compositions comprising fatty acidesters of alkanols) derived from such fatty acid mixtures can be usefulin the compositions of the present invention without need to firstseparate the fatty acid esters. For reason of cost, not separating thefatty acid esters is preferred. Also, the presence of a range of chainlengths and unsaturation instead of a single, saturated chain lengthfacilitates maintaining, at typical storage and use temperatures of atleast 15° C., component (c) in pure form as a clear liquid and in thecomposition as a liquid not containing alkanol fatty acid ester solids.Therefore preferred is the present composition wherein component (c) inits isolated form (i.e. not part of the composition) has a cloud point(according to ASTM Standard Method D2500 (1994)) less than 15° C. Cloudpoint is the temperature at which small crystals form in a liquid. Alsopreferred is the composition at a temperature of at least 15° C., whichwill ensure the absence of alkanol fatty acid ester solids if component(c) has a cloud point of less than 15° C.

Suitable alkanol fatty acid ester compositions obtained fromplant-derived starting materials include seed and fruit oils ofsunflower, rapeseed, olive, corn, soybean, cotton, oil palm, coconut andlinseed. Of note is a composition of the invention wherein the one ormore fatty acid esters of alkanols (i.e. component (c)) comprise fattyacid methyl esters derived from seed oils of sunflower, soybean,rapeseed, cotton, linseed, oil palm or coconut (including mixturesthereof). Of particular note is a composition of the invention whereincomponent (c) comprises fatty acid methyl esters derived from seed oilsof soybean, rapeseed or coconut (including mixtures thereof). Methylatedsoybean, rapeseed and coconut oils have cloud points near 0° C. Also ofparticular note is a composition of the invention wherein the one ormore fatty acid esters of alkanols (i.e. component (c)) comprise fattyacid methyl esters derived from soybean oil (also known as methylatedsoybean oil or methyl soyate). One example of fatty acid methyl estersderived from soybean oil is AGNIQUE ME 18 SD (including the product madein the U.S.A. and marketed as AGNIQUE ME 18 SD-U) from BASF. Also ofnote is component (c) comprising methylated coconut oil, particularly incombination with methylated soybean oil to provide a wide range of fattyacid esters. Methylated coconut oil has a high degree of saturation(absence of carbon-carbon double bonds) and thus is more resistant tooxidation than many other methylated seed oils.

Fatty acid esters of alkanols and methods for their preparation are wellknown in the art. For example, “biodiesel” typically comprises fattyacid esters of ethanol or more commonly methanol. Two principal routesused to prepare fatty acid alkanol esters are transesterificationstarting with another fatty acid ester (often a naturally occurringester with glycerol) and direct esterification starting with the fattyacid. A variety of methods are known for these routes. For example,direct esterification can be accomplished by contacting a fatty acidwith an alkanol in the presence of a strong acid catalyst such assulfuric acid. Transesterification can be accomplished by contacting astarting fatty acid ester (e.g., a triglyceride) with the alcohol in thepresence of a strong acid catalyst such as sulfuric acid but morecommonly a strong base such as sodium hydroxide.

Alkylated seed oils are the transesterification products of seed oilswith an alkanol. For example methylated soybean oil, also known asmethyl soyate, comprises methyl esters produced by thetransesterification of soybean oil with methanol. Methyl soyate thuscomprises methyl esters of fatty acids in the approximate molar ratiothat the fatty acids occur esterified with glycerol in soybean seed oil.Alkylated seed oils such as methyl soyate can be fractionally distilledto modify the proportion of methyl fatty acid esters, but suchmodification of the proportion of methyl fatty acid esters typicallyprovides no advantage for the composition of the present invention.However, distillation can be beneficial for providing a purifiedalkylated seed oil. AGNIQUE ME 18 SD (including the U.S.A.-made productAGNIQUE ME 18 SD-U) consists of distilled methylated soybean oil.

In the present composition, the liquid carrier comprises as component(c) one or more fatty acid esters of C₁-C₄ alkanols, typically as themain (i.e. greater than 50% by weight) constituent of the liquidcarrier. Therefore component (c) can be considered to form the liquidcarrier. Components of the composition having good solubility in alkanolfatty acid esters are typically mostly or completely dissolved in theliquid carrier. In contrast, components of the composition, such ascomponents (a) and (b), having low solubility in alkanol fatty acidesters are typically dispersed as solid particles in the liquid carrier.Because fatty acid esters of C₁-C₄ alkanols have relatively lowviscosity compared to vegetable oils, they provide a liquid carrierhaving low viscosity, which improves the pourability of the presentcomposition, thus facilitating dispensing. Besides providing the liquidcarrier for the components of the invention either dissolved ordispersed, the fatty acid esters of C₁-C₄ alkanols also can help providerainfastness after the composition has been diluted with water, sprayedon foliage of vegetation to be controlled, and spray water evaporated.

The present composition includes as component (d) one or moresurfactants having an emulsifier property (i.e. emulsifiers) in theamount of 5 to 25% of the composition by weight. More typically,component (d) is at least 10%, but not more than 20% of the compositionby weight.

The term “surfactant” is a shortened form of the term “surface-activeagent”. Surfactants have the useful tendency to migrate to interfaces(e.g., oil-water, air-water, water-solid) surfaces, resulting in agreater concentration at the interface than the surrounding bulk liquidphase. The propensity of surfactants to migrate to interfaces resultsfrom the combination of at least one hydrophobic (water-insoluble) groupwith at least one hydrophilic (water-soluble) group in the surfactantmolecule. The hydrophobic group is also referred to as the lipophilicgroup or as the hydrophobe in many publications, because this group issoluble in liquids having low polarity, such as the fatty acid esters ofC₁-C₄ alkanols of present component (c).

Although surfactants share the general tendency to migrate tointerfaces, their properties can differ significantly, depending on themolecular structures of their hydrophobic and hydrophilic groups.Depending upon the structures of these surfactant molecule groups andthe other components (e.g., solvents) present in thesurfactant-containing medium, surfactants may have utility hasemulsifying agents (i.e. emulsifiers), dispersing agents (i.e.dispersants), wetting agents, or foaming, anti-foaming or defoamingagents. Surfactants may have multiple functionalities, leading tomultiple uses.

In the present composition, the liquid carrier is formed by one or morefatty acid esters of C₁-C₄ alkanols, which with low polarity, have verylittle solubility in water. Because the present herbicidal compositionis typically first diluted with much greater amount of water in a spraysystem before application to the undesired vegetation to be controlled,for satisfactory performance the alkanol fatty acid ester component (c)in the present composition needs to form an oil-in-water emulsion whenthe composition is diluted with water. Component (d) is included topromote forming this emulsion. Therefore the one or more surfactants incomponent (d) must have an emulsifier property, specifically the abilityto promote the formation of oil-in-water emulsions. The one or moresurfactants in component (d) can also have, in addition, othersurfactant utilities (e.g., wetting agent), but they must havesignificant ability to promote the formation of oil-in-water emulsionsto be considered constituents of component (d).

Surfactants useful for forming oil-in-water emulsions are well known inthe art. An extensive listing of commercially available surfactants,their chemical class and typical utility is given in McCutcheon'sDetergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, N.J.,as well as Sisely and Wood, Encyclopedia of Surface Active Agents,Chemical Publ. Co., Inc., New York, 1964.

In addition to categorization of surfactants by functionality,functional classes are commonly further categorized according to thetype of ion, or lack thereof, that the surfactant forms on addition towater, i.e. anionic, non-ionic or cationic. For the anionic and cationicsubclasses, the ionic charge of significance in the classification isthe charge on the hydrophilic moiety in the molecule, not thecounterion. Typically in molecules of anionic or cationic surfactants,the charged hydrophilic group is the smallest portion of the molecule.In the molecules of non-ionic surfactants, the hydrophilic group ispolar, but does not ionize.

The molecules of anionic surfactants have a hydrophilic group thationizes to form an anion (negatively charged ion) when placed in anaqueous solution. Carboxylate, sulfate, sulfonate and phosphate are themost common hydrophilic groups in anionic surfactant molecules. Examplesof anionic surfactants include: sodium alkylnaphthalene sulfonates,naphthalenesulfonate formaldehyde condensates, alkylbenzenesulfonates,lignin sulfonates, alkyl sulfates, alkyl ether sulfates, dialkylsulfosuccinates, polycarboxylates, phosphate esters, ethoxylatedtristyrylphenol phosphate salts and alkali salts of fatty acids.

The molecules of cationic surfactants have a hydrophilic group thationizes to form a cation (positively charged ion) when placed in anaqueous solution. Examples of cationic surfactants include quaternaryammonium salts such as ethoxylated fatty amines, benzylalkylammoniumsalts, pyridinium salts and quaternary imidazolium compounds.

The molecules of non-ionic surfactants have a hydrophilic group that ispolar but does not contain an ionizable functionality. Examples ofnon-ionic surfactants include: alkoxylated triglycerides; sorbitol andfatty acid esters, including their ethoxylates; ethoxylated sorbitanfatty acid esters; alkoxylated aliphatic alcohols; alkoxylated mono-,di- and tri-alkylphenols; alkoxylated mono-, di- and tri-styryl phenols;ethoxy, propoxy and butoxy block and random copolymers, such aspolyoxyethylene-polyoxypropylene (EO/PO) block copolymers; andalkylpolyglycosides; wherein the term “alkoxylated” refers to thepresence of one or more alkylene oxide-derived units, e.g., one or moreunits such as oxyethylene units (—OCH₂CH₂—) derived from ethylene oxide,oxypropylene units (—OCH(CH₃)CH₂—) derived from propylene oxide, andoxybutylene units (—OCH(CH₂CH₃)CH₂—) derived from butylene oxide. Theprefix “poly” is often included in the name of a surfactant subclass orspecific surfactant itself, if on average, more than one oxyalkyleneunit is present in each surfactant molecule, e.g., “polyoxyethylene” and“polyoxypropylene”. Alternatively, a “POE” or “POP” number may beincluded in the name to indicate the number of polyoxyethylene orpolyoxypropylene, respectively, units present on average in eachmolecule.

To form present component (d), both anionic and non-ionic surfactants,particularly mixtures of these two general classes, are found to beuseful. Anionic surfactants and non-ionic surfactants can be selectedbased on their reported utility as oil-in-water emulsifiers. Non-ionicsurfactants can be also selected based on their HLB(Hydrophile-Lipophile Balance) values.

The HLB system or index is well known to those skilled in the art. HLBvalues for non-ionic surfactants are readily available in textbooks(e.g., A. W. Adamson, Physical Chemistry of Surfaces, John Wiley andSons, 1982), and product technical data sheets and bulletins fromcommercial suppliers.

The HLB system is loosely based on the type and size of a surfactantmolecule's hydrophobic and hydrophilic moieties and qualitatively trendswith the polarity of the surfactant molecule. The HLB scale ranges fromabout 1 to 40, with the most commonly used non-ionic surfactants havingvalues between 1 and 20. Increasing HLB indicates increasinghydrophilicity, e.g., increasing potential for the surfactant moleculespresent in an oil-water interface to increase the statisticaldistribution of their position and orientation in the interface so thatthe surfactant molecule on average penetrates deeper into the waterphase as the HLB increases. Ranges of HLB values and the correspondingbehaviors of non-ionic surfactants typically observed on addition towater are: less than 7, poor or no dispersibility in water(hydrophobic); greater than 12, clear solutions in water (hydrophilic);between 7 and 12, showing a progressive transition with increasing HLB,going from coarse, milky white, relatively unstable dispersions in waterto cloudy and, in some cases, translucent emulsions, having improvedstability against coalescence and phase separation. As constituentsuseful in present component (d) having an emulsifier property, non-ionicsurfactants typically have HLB values in the range of about 8 to about12. However, blends of non-ionic surfactants having HLB values in therange of about 8 to about 12 are also useful even if the HLB values ofthe individual surfactants are outside of this range.

The HLB value of non-ionic surfactant blends can be determined bycalculating the mass-weighted average HLB of the mixture. Thus the HLBvalue of the mixture equals the sum calculated by adding the product ofthe weight fraction of each constituent multiplied by the HLB of theconstituent. For example, a 4:1 by weight mixture of TOXIMUL 2464F (HLB9) with TOXIMUL 8240 (HLB 13) would have an HLB of 9.8, i.e.(0.8×9)+(0.2×13), where 0.8 is the fraction of 3464F in the mixture and9 is its HLB value, and 0.2 is the fraction of 8240F in the mixture and13 is its HLB value.

A wide range of anionic and non-ionic surfactants having utility foroil-in-water emulsions are suitable for forming component (d) of thepresent composition. Optimal selection of these surfactants forcomponent (d) can be achieved through simple experimentation involvingforming mixtures of the surfactants evaluated with one or more fattyacid esters of C₁-C₄ alkanols in various ratios, then adding themixtures in an amount of about 1% to about 2% by weight of each towater, followed by thorough mixing and subsequent assessment of thequality and type of emulsion that forms.

Anionic surfactants of note as constituents of present component (d) arealkylbenzenesulfonates and alkylnaphthalenesulfonates. (These chemicalclasses of anionic surfactants are alternatively identified by namesinserting one or more spaces, e.g., “alkylbenzene sulfonates”, “alkylbenzene sulfonates”, “alkylnaphthalene sulfonates”, “alkyl naphthalenesulfonates”.) Examples of alkylbenzenesulfonates andalkylnaphthalene-sulfonates include calcium dodecylbenzenesulfonate(e.g., RHODACAL 70/B (Rhodia), PHENYLSULFONAT CA100 (Clariant)),isopropylammonium dodecylbenzenesulfonate (e.g., ATLOX 3300B (Croda))and sodium diisopropyl naphthalenesulfonate (e.g., MORWET IP (DeSoto)).

Non-ionic surfactants of note as constituents of present component (d)are ethoxylated triglycerides, ethoxylated tri-styryl phenols,ethoxylated aliphatic alcohols, ethoxylated sorbitan mono- andtri-esters, ethoxylated sorbitol hexa-esters andpolyoxyethylene-polyoxypropylene block copolymers. Commerciallyavailable ethoxylated triglycerides are typically produced byethoxylating seed oils (e.g., from soybean, rapeseed or castor bean)with from 10 to 40 moles of ethylene oxide. Examples of ethoxylatedtriglycerides include ethoxylated castor oil (e.g., TOXIMUL 8240F andTOXIMUL 8242F (Stepan), EMULSOGEN EL 360 (Clariant)) and ethoxylatedsoybean oil (e.g., AGNIQUE SBO-10 and AGNIQUE SBO-30 (Cognis, nowBASF)). Commercially available ethoxylated tri-styryl phenolsparticularly useful for present component (d) typically contain anaverage of about 10 to about 20 oxyethylene units. Examples ofethoxylated tri-styryl phenol products include EMULSOGEN TS 160(Clariant) and SOPROPHOR BSU (Rhodia). Ethoxylated aliphatic alcohols(also known as fatty alcohol ethoxylates) are generally prepared fromC₈-C₂₂ alkanols or alkenols, which may be branched but are moretypically linear. Commercially available ethoxylated aliphatic alcoholsparticularly useful for present component (d) typically contain anaverage of about 3 to about 15 oxyethylene units. Examples ofethoxylated aliphatic alcohol products include SYNPERONIC All (Uniqema)and GENAPOL LA 070 (Clariant). Examples of ethoxylated sorbitan mono-and tri-esters include polyoxyethylene (4) sorbitan monolaurate (e.g.,TWEEN 21 (Croda)) and polyoxyethylene (20) sorbitan tristearate (TWEEN65 (Croda)). Examples of ethoxylated sorbitol hexa-esters includepolyoxyethylene (40) sorbitol hexaoleate (e.g,. ATLAS G-1086 (Croda)).Examples of polyoxyethylene-polyoxypropylene block copolymers includePLURONIC F108 (BASF), and ATLOX 4912, ATLAS G-5000 (Croda) andSYNPERONIC PE Series copolymers (Croda). Of note also are combinationsof surfactants in these non-ionic surfactant classes, particularly toprovide non-ionic surfactant blends with an HLB value of 8 to 12.

Combinations of surfactants (i.e. surfactant blends) have beendiscovered to work well for component (d) to emulsify the one or morefatty acid esters of C₁-C₄ alkanols of component (c) on dilution withwater. Of particular note is present component (d) consisting of amixture of surfactant constituents, each having an emulsifier property,wherein at least one surfactant constituent is selected from anionicsurfactants, such as a calcium or magnesium salt of analkylbenzenesulfonate, and at least one surfactant constituent isselected from non-ionic surfactants, such as apolyoxyethylene-polyoxypropylene block copolymer. Other non-ionicsurfactants, also typically comprising ethoxylation, are useful in thesecombinations as well. In the combination of an anionic surfactant with anonionic surfactant, the anionic surfactant is often the primaryemulsifier, but the nonionic surfactant further assists theemulsification process and provides emulsion stability. Besides havingan emulsifier property, the nonionic surfactant can often act as adefoamer to counteract the foaming property of the anionic surfactantand can also act as a wetting agent to further improve biologicalperformance. Certain anionic and non-ionic surfactants can also helpdisperse particulates. Combinations of anionic and non-ionic surfactantsare commercially available, thus obviating need for the formulator tomix separate constituents. Examples of such non-ionic/ionic surfactantblends include ATPLUS 300F (Croda) and Emulsogen ITL (Clariant).

The present composition optionally further includes (e) up to 40% of oneor more biologically active agents other than metsulfuron-methyl andthifensulfuron-methyl. When component (e) is present, typically it is atleast 0.1% and more typically at least 5%, 10%, 15%, 20% or 35% of thecomposition by weight. Also, when component (e) is present, typically itis not more than 35%, more typically not more than 30%, of thecomposition by weight.

The other biologically active agents of component (e) may includeherbicides other than metsulfuron-methyl and thifensulfuron-methyl, andmay also include herbicide safeners, plant growth regulants,insecticides, insect antifeedants, miticides, nematocides, bactericidesand fungicides, including both chemical and biological agents. Mostcommonly, the other active biologically agents of component (e) areherbicides or herbicide safeners. Examples of herbicides includeacetochlor, acifluorfen and its sodium salt, aclonifen, acrolein(2-propenal), alachlor, alloxydim, ametryn, amicarbazone, amidosulfuron,aminocyclopyrachlor and its esters (e.g., methyl, ethyl) and salts(e.g., sodium, potassium), aminopyralid, amitrole, ammonium sulfamate,anilofos, asulam, atrazine, azimsulfuron, beflubutamid, benazolin,benazolin-ethyl, bencarbazone, benfluralin, benfuresate,bensulfuron-methyl, bensulide, bentazone, benzobicyclon, benzofenap,bicyclopyrone, bifenox, bilanafos, bispyribac and its sodium salt,bromacil, bromobutide, bromofenoxim, bromoxynil and its esters such asbromoxynil heptanoate and bromoxynil octanoate, butachlor, butafenacil,butamifos, butralin, butroxydim, butylate, cafenstrole, carbetamide,carfentrazone-ethyl, catechin, chlomethoxyfen, chloramben,chlorbromuron, chlorflurenol-methyl, chloridazon, chlorimuron-ethyl,chlorotoluron, chlorpropham, chlorsulfuron, chlorthal-dimethyl,chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, clacyfos,clefoxydim, clethodim, cyclopyrimorate, clodinafop-propargyl, clomazone,clomeprop, clopyralid, clopyralid-olamine, cloransulam-methyl,cumyluron, cyanazine, cycloate, cyclopyrimorate, cyclosulfamuron,cycloxydim, cyhalofop-butyl, 2,4-D and its butotyl, butyl, isoctyl andisopropyl esters and its dimethylammonium, diolamine and trolaminesalts, daimuron, dalapon, dalapon-sodium, dazomet, 2,4-DB and itsdimethylammonium, potassium and sodium salts, desmedipham, desmetryn,dicamba and its diglycolammonium, dimethylammonium, potassium and sodiumsalts, dichlobenil, dichlorprop, diclofop-methyl, diclosulam,difenzoquat metilsulfate, diflufenican, diflufenzopyr, dimefuron,dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P,dimethipin, dimethylarsinic acid and its sodium salt, dinitramine,dinoterb, diphenamid, diquat dibromide, dithiopyr, diuron, DNOC,endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron-methyl,ethiozin, ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid,fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenoxasulfone, fenquinotrione,fentrazamide, fenuron, fenuron-TCA, flamprop-methyl,flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam,fluazifop-butyl, fluazifop-P-butyl, fluazolate, flucarbazone,flucetosulfuron, fluchloralin, flufenacet, flufenpyr, flufenpyr-ethyl,flumetsulam, flumiclorac-pentyl, flumioxazin, fluometuron,fluoroglycofen-ethyl, flupoxam, flupyrsulfuron-methyl and its sodiumsalt, flurenol, flurenol-butyl, fluridone, flurochloridone, fluroxypyrand its esters such as fluroxypyr-meptyl, flurtamone, fluthiacet-methyl,fomesafen, foramsulfuron, fosamine-ammonium, glufosinate,glufosinate-ammonium, glufosinate-P, glyphosate and its salts such asammonium, isopropylammonium, potassium, sodium (including sesquisodium)and trimesium (alternatively named sulfosate), halauxifen,halauxifen-methyl, halosulfuron-methyl, haloxyfop-etotyl,haloxyfop-methyl, hexazinone, imazamethabenz-methyl, imazamox, imazapic,imazapyr, imazaquin, imazaquin-ammonium, imazethapyr,imazethapyr-ammonium, imazosulfuron, indanofan, indaziflam,iofensulfuron, iodosulfuron-methyl, ioxynil, ioxynil octanoate,ioxynil-sodium, ipfencarbazone, isoproturon, isouron, isoxaben,isoxaflutole, isoxachlortole, lactofen, lenacil, linuron, maleichydrazide, MCPA and its salts (e.g., MCPA-dimethylammonium,MCPA-potassium and MCPA-sodium, esters (e.g., MCPA-2-ethylhexyl,MCPA-butotyl) and thioesters (e.g., MCPA-thioethyl), MCPB and its salts(e.g., MCPB-sodium) and esters (e.g., MCPB-ethyl), mecoprop, mecoprop-P,mefenacet, mefluidide, mesosulfuron-methyl, mesotrione, metam-sodium,metamifop, metamitron, metazachlor, metazosulfuron, methabenzthiazuron,methylarsonic acid and its calcium, monoammonium, monosodium anddisodium salts, methyldymron, metobenzuron, metobromuron, metolachlor,S-metolachlor, metosulam, metoxuron, metribuzin, molinate, monolinuron,naproanilide, napropamide, napropamide-M, naptalam, neburon,nicosulfuron, norflurazon, orbencarb, orthosulfamuron, oryzalin,oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen,paraquat dichloride, pebulate, pelargonic acid, pendimethalin,penoxsulam, pentanochlor, pentoxazone, perfluidone, pethoxamid,pethoxyamid, phenmedipham, picloram, picloram-potassium, picolinafen,pinoxaden, piperophos, pretilachlor, primisulfuron-methyl, prodiamine,profoxydim, prometon, prometryn, propachlor, propanil, propaquizafop,propazine, propham, propisochlor, propoxycarbazone, propyrisulfuron,propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen-ethyl,pyrasulfotole, pyrazogyl, pyrazolynate, pyrazoxyfen,pyrazosulfuron-ethyl, pyribenzoxim, pyributicarb, pyridate, pyriftalid,pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium,pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine,quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-P-tefuryl, rimsulfuron,saflufenacil, sethoxydim, siduron, simazine, simetryn, sulcotrione,sulfentrazone, sulfometuron-methyl, sulfosulfuron, 2,3,6-TBA, TCA,TCA-sodium, tebutam, tebuthiuron, tefuryltrione, tembotrione,tepraloxydim, terbacil, terbumeton, terbuthylazine, terbutryn,thenylchlor, thiazopyr, thiencarbazone, thiobencarb, tiafenacil,tiocarbazil, tolpyralate, topramezone, tralkoxydim, tri-allate,triafamone, triasulfuron, triaziflam, tribenuron-methyl, triclopyr,triclopyr-butotyl, triclopyr-triethylammonium, tridiphane, trietazine,trifloxysulfuron, trifludimoxazin, trifluralin, triflusulfuron-methyl,tritosulfuron, vernolate,3-(2-chloro-3,6-difluorophenyl)-4-hydroxy-1-methyl-1,5-naphthyridin-2(1H)-one,5-chloro-3-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-1(4-methoxyphenyl)-2(1H)-quinoxalinone,2-chloro-N-(1-methyl-1H-tetrazol-5-yl)-6-(trifluoromethyl)-3-pyridinecarboxamide,7-(3,5-dichloro-4-pyridinyl)-5-(2,2-difluoroethyl)-8-hydroxypyrido[2,3-b]pyrazin-6(5H)-one,4-(2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone),5-[[(2,6-difluorophenyl)-methoxy]methyl]-4,5-dihydro-5-methyl-3-(3-methyl-2-thienyl)isoxazole,3-[7-fluoro-3,4-dihydro-3-oxo-4-(2-propyn-1-yl)-2H-1,4-benzoxazin-6-yl]dihydro-1,5-dimethyl-6-thioxo-1,3,5-triazine-2,4(1H,3H)-dione,4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5(2H,4H)-dione,methyl4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoro-2-pyridinecarboxylate,2-methyl-3-(methyl-sulfonyl)-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoromethyl)benzamide and2-methyl-N-(4-methyl-1,2,5-oxadiazol-3 -yl)-3-(methylsulfinyl)-4-(trifluoromethyl)benzamide. Other herbicides alsoinclude bioherbicides such as Alternaria destruens Simmons,Colletotrichum gloeosporiodes (Penz.) Penz. & Sacc., Drechsieramonoceras (MTB-951), Myrothecium verrucaria (Albertini & Schweinitz)Ditmar: Fries, Phytophthora palmivora (Butl.) Butl. and Pucciniathlaspeos Schub. Examples of herbicide safeners include allidochlor,benoxacor, cloquintocet-mexyl, cyometrinil, cyprosulfonamide,dichlormid, dicyclonon, dietholate, dimepiperate, fenchlorazole-ethyl,fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-ethyl,mefenpyr-diethyl, mephenate, methoxyphenone naphthalic anhydride(1,8-naphthalic anhydride), oxabetrinil,N-(aminocarbonyl)-2-methylbenzenesulfonamide,N-(amino-carbonyl)-2-fluorobenzenesulfonamide,1-bromo-4-[(chloromethyl)sulfonyl]benzene (BCS),4-(dichloroacetyl)-1-oxa-4-azospiro[4.5]decane (MON 4660),2-(dichloromethyl)-2-methyl-1,3-dioxolane (MG 191), ethyl1,6-dihydro-1-(2-methoxyphenyl)-6-oxo-2-phenyl-5-pyrimidinecarboxylate,2-hydroxy-N,N-dimethyl-6-(trifluoromethyl)pyridine-3-carboxamide, and 3-oxo-1-cyclohexen-1-yl1-(3,4-dimethylphenyl)-1,6-dihydro-6-oxo-2-phenyl-5-pyrimidinecarboxylate.

Of note as biologically active agents in component (e) of the presentcomposition are biologically active chemical compounds, such asherbicides or herbicide safeners, that are liquids or solids having amelting point less than 100° C., particularly less than 90° C., 80° C.or 70° C., and most particularly not greater than 60° C., because liquidand low-melting solid biologically active compounds are difficult toformulate in solid compositions. In the present composition, suchliquids and low-melting solids typically dissolve in the liquid carrierformed by component (c). Also of note in component (e) of the presentcomposition are biologically active agents typically applied atapplication rates of at least 100 g/ha when applied alone, because theirhigher application rates necessitate their concentrations to becorrespondingly much greater than the concentration ofmetsulfuron-methyl in the present composition, which then requires theconcentration of metsulfuron-methyl to be not more than 1% by weight,resulting in excessive decomposition on storage in the absence of astabilizer, such as thifensulfuron-methyl as now discovered.

Of particular note in this regard as possible constituents of component(e) are fluroxypyr esters and bromoxynil esters.

When one or more fluroxypyr esters are present in the composition, thefluroxypyr ester constituent is typically at least 5%, more typically atleast 15% and not more than 40%, more typically not more than 25% byweight of the composition. Examples of fluroxypyr esters includefluroxypyr-2-butoxy-1-methyethyl (2-butoxy-1-methylethyl[(4-amino-3,5-dichloro-6-fluoro-2-pyridinyl)oxy]acetate), which is aliquid at room temperature, and fluroxypyr-meptyl (1-methylheptyl[(4-amino-3,5-dichloro-6-fluoro-2-pyridinyl)oxy]-acetate), which meltsat 58.2-60° C.

When one or more bromoxynil esters are present in the composition, thebromoxynil ester constituent is typically at least 5%, more typically atleast 25% and not more than 40%, more typically not more than 35% of thecomposition by weight. Typically the bromoxynil esters are C₆-C₁₀alkanoate esters of bromoxynil. Examples of bromoxynil esters includebromoxynil heptanoate (2,6-dibromo-4-cyanophenyl heptanoate) andbromoxynil octanoate (2,6-dibromo-4-cyanophenyl octanoate), which meltsat 45-46° C.

The present composition optionally further includes (f) up to 63% of oneor more additional formulating ingredients, alternatively described asauxiliaries, not otherwise corresponding to components (a) through (e).Examples of additional formulating ingredients are surfactants nothaving a significant emulsifier property, thickening agents, liquid andsolid diluents, dyes, drying agents and the like. These ingredients areknown to one skilled in the art and can be found described, for example,in McCutcheon's 2001, Volume 2: Functional Materials published by MCPublishing Company.

When component (f) is present, typically it is at least 0.1%, and moretypically at least 1%, 2% or 3% of the composition by weight. Also, whencomponent (f) is present, more typically it is not more than 50%, 40%,30%, 20%, 15% or 10% of the composition by weight to accommodatesubstantially greater than minimal amounts of components (a) through(e).

Of note as examples of possible additional formulating ingredients aresurfactants not having a significant emulsifier property, as well asthickening agents. Of note is a composition of the invention whereincomponent (f) comprises at least one constituent selected from (1) fromsurfactants not having a significant emulsifier property, particularlysurfactants having a dispersant property, and (2) thickening agents. Ofparticular note is a composition of the invention wherein component (f)comprises at least one constituent selected from (1) surfactants nothaving a significant emulsifier property, particularly surfactantshaving a dispersant property, and also at least one constituent selectedfrom (2) thickening agents.

When solid particulates, such as particles of present components (a) and(b), are in suspension, whether oil-based (e.g., suspended in the one ormore fatty acid esters of C₁-C₄ alkanols of present component (c)) oraqueous-based (e.g., suspended in water after dilution of the presentcomposition with water), their kinetic energy and trajectory can forcethem close enough together such that their mutual attractive forcesovercome their mutual repulsive forces. In some instances, this canresult in a flocculation or coagulation of the particles, i.e. they canloosely stick together (“weak flocculation”) or irreversibly agglomerate(“coagulation”). Dispersing agents, also called dispersants, aresurfactants that can influence (e.g., reduce) the degree to which bothorganic and inorganic particulate solids interact and thereby stabilizetheir suspension.

Dispersing agents are generally either anionic or non-ionic surfactantsand are often polymeric. Anionic dispersing agents includealkylnaphthalene sulfonates and their formaldehyde condensates (e.g.,MORWET D425), polyalkylaryl sulfonates (e.g., SUPRAGIL MNS90),polymerized fatty acids (e.g., ATLOX LP-1 (12-hydroxyoctadecanoic acidhomopolymer, octadecanoate), ricinoleic acid homopolymer), ligninsulfonates (e.g., ammonium lignosulfonate or sodium lignosulfonate),polyphenol sulfonates and the salts of polyacrylic acids. Non-ionicdispersing agents include phosphate esters of tristyrylphenolethoxylates (e.g., SOPROPHOR 3D33, ethoxylated triglycerides,ethoxylated aliphatic alcohols, polyoxyethylene-polyoxypropylene (EO/PO)block copolymers (e.g., PLURONIC F108, ATLOX 4912, ATLAS G-5000,SYNPERONIC PE Series copolymers) and ethylene oxide-propylene oxidebased acrylic acid graft copolymers such as methyl methacrylate graftcopolymers (e.g., ATLOX 4913).

As already mentioned, surfactants generally modify the surface tensionof a liquid, and depending on the nature of the hydrophilic andlipophilic groups in a surfactant molecule, surfactants can be useful asemulsifying agents (i.e. emulsifiers), dispersing agents (i.e.dispersants), wetting agents or antifoaming agents (i.e. defoamers).Furthermore, depending upon molecular structure, a particular surfactantmay have more than one useful surfactant property. For example, asurfactant may be useful as a both an emulsifier and a dispersant.

In the context of the present disclosure and claims, a surfactant havingan emulsifier property, i.e., an emulsifier, is a surfactant known to beuseful for forming oil-in-water emulsions. Furthermore, a surfactanthaving an emulsifier property is considered to be a constituent ofcomponent (d) irrespective of whether it may also be useful as adispersing agent, wetting agent or defoamer.

Inclusion in present component (f) of one or more surfactants having adispersant property but not an emulsifier property is optional,particularly if one or more surfactants of component (d) have adispersant property in addition to an emulsifier property. Examples ofsurfactants having both emulsifier properties and dispersant propertiesinclude alkylnaphthalene sulfonates, ethoxylated triglycerides,ethoxylated aliphatic alcohols and polyoxyethylene-polyoxypropyleneblock copolymers. However, including a surfactant optimized for adispersant property while having no significant emulsifier property canachieve optimum results for preventing flocculation and coagulation ofcomponents (a) and (b) in the liquid carrier formed by component (c)and/or the aqueous mixture for spraying formed after dilution of thepresent composition in water. When such a dispersant is present in thecomposition, it is typically at least 0.1%, more typically at least 2%of the composition by weight. Also when a dispersant is present in thecomposition, it is typically not more than 5% of the composition byweight. Polymerized fatty acids such as ATLOX LP-1 have been found towork particularly well in such amounts as dispersants in the presentcomposition.

Component (f) may also comprise surfactants having additional usefulproperties other than an emulsifier property, such as wetting agents andanti-foam agents.

Although optional, particularly if the present composition is used soonafter preparation, typically one or more thickening agents (also knownas thickeners, rheology modifiers or suspending agents) are included aspart of component (f) to prevent undesirable phase separation and/orsedimentation of solid particles (e.g., of components (a) and (b)) thatcan occur in unstructured suspension concentrates during storage.Thickening agents increase the viscosity of the continuous liquid mediumin which solid particles (e.g., of components (a) and (b)) are suspendedand thus reduce their propensity to settle and form a separated, compactsediment during storage. Also, a thickening agent may improve theefficiency of a wet milling process used to prepare the presentcomposition. When a thickening agent is present is the composition, itis typically at least 0.1%, more typically at least 0.5%, of thecomposition by weight. Also when a thickening agent is present,typically it is not more than 5%, and more typically not more than 4%,3% or 2% of the composition by weight.

Thickening agents are well known in the art of formulations. For thepresent composition having a liquid carrier comprising one or more fattyacid esters of C₁-C₄ alkanols, thickening agents are generally selectedfrom silicas and silicates, which may be naturally occurring,artificially produced, or organically modified.

Silicas include synthetic precipitated or fumed silicas, which may bechemically (including organically) modified, for example withdimethyldichlorosilane, to increase hydrophobicity. Such silicas arecommercially available under a variety of trade names (e.g., SIPERNAT orAEROSIL (Evonick), CAB-O-SIL (Cabot)). An example of a hydrophobic fumedsilica treated with dimethyldichlorosilane is AEROSIL R974 (Evonik).

Silicates include phyllosilicate minerals having particles of less than2μm size present in naturally occurring clays, such as kaolinite andsmectites (e.g., smectite, hectorite, attapulgite, montmorillonite), andtheir combinations such as bentonites. Clays comprising minerals of thesmectite group generally can be organically chemically modified bycation exchange of metal ions with organic salts such as quaternaryammonium salts to increase hydrophobicity. Natural and modified claysare commercially available under a variety of trade names (e.g., BENTONE(Elementis), BARDEN clay (Kentucky Tennessee Clay Co.), ATTAGEL (BASF),MIN-U-GEL (Active Minerals)). Organic chemical modification of claysthrough surface treatment with quaternary ammonium salts renders themmore effective for rheology modification (particularly thickening underlow-shear conditions) in non-aqueous systems, such as the liquid phaseof the present composition formed from one or more fatty acid esters ofC₁-C₄ alkanols (i.e. component (c)). Examples of organically modifiedclays include GARAMITE 1958 and CLAYTONE 40 (Southern Clay Products) andBENTONE 34 and BENTONE 1000 (Elementis). Organically modified clays workparticularly well as thickening agents in the present composition. Ofnote is the composition of the present invention comprising by weight0.5 to 5% of one or more organically modified clays.

As already noted, the present composition has a single liquid phasewherein the liquid carrier comprises as component (c) one or more fattyacid esters of C₁-C₄ alkanols. The single liquid phase requirementprecludes the presence of liquid phases in addition to the continuousliquid phase formed by component (c). Therefore while solid particles,such as of components (a) and (b) can be suspended as a dispersion inthe liquid phase formed by component (c), liquid droplets of othersubstances cannot be present, such as in an emulsion, in the liquidphase. Therefore any water that is present in the composition must bedissolved in the liquid phase formed by component (c) or absorbed intoparticles of solid substances suspended in the liquid phase, but notpresent as an emulsion. This inherently greatly limits the amount ofwater that can be present.

Even for technical grade fatty acid esters of C₁-C₄ alkanols containingpolar impurities, e.g., biodiesel, the solubility of water at roomtemperature is typically less than 2% by weight. Although otheringredients in the present composition may accommodate additional waterwhile maintaining a single liquid phase, generally the presentcomposition does not contain more than 10% water by weight, andtypically not more than 5% water by weight. Lesser amounts of water maybe advantageous for better stability of the ingredients, so preferablythe present composition does not contain more than 3%, 2% or even 1%water by weight.

The present composition can be easily prepared by combining thecomponent ingredients and reducing the particle size of insolublecomponents (e.g., components (a) and (b)) in the liquid carrier formedby component (c). As is well known in the art, particle size reductionof insoluble components in an oil dispersion can be beneficial forproviding stable homogeneous suspensions, as well as maximizingbioefficacy of the composition. Generally to produce stable suspensions,the size of particles in the suspension should be not greater than 50μm, preferably not greater than 10 μm, and most preferably not greaterthan 5 μm. Typically the size of the particles is at least 1 μm.

A variety of methods for reducing particle size of insoluble componentsin oil dispersions are known in the art and suitable for preparing thepresent composition. These include ball-milling, bead-milling,sand-milling, colloid-milling and air-milling combined with high-speedblending. Ball-, bead- and sand-mills are media mills that achieve sizereduction of particles by vigorous agitation with grinding media (e.g.,balls or beads made of glass or ceramic, or sand). In ball-mills,typically the container rotates, while in bead- or sand-mills, grindingis achieved by an impeller in the grinding media. In horizontalbead-mills, agitation is by the action of an internal agitator rapidlyrotating along the axis of the milling chamber. Colloid mills achievesize reduction of particles by passing the material to be ground througha narrow gap of a rapidly rotating rotor-stator assembly. Ball-milling,bead-milling, sand-milling and colloid-milling generally involvewet-milling (i.e. the liquid carrier is present). Air-milling issuitable for dry powders (e.g., present components (a) and (b)), whichwould then be combined with liquid components (e.g., present component(c)) and high-speed blended using high-speed impellers or dispersators(i.e. rotor-stator). For sake of convenience, the present components canbe combined before milling.

Thus in this process for preparing the composition of the invention,components (a) and (b) are milled together in a liquid carriercomprising components (c) and (d), and any other components (e.g.,component (e) and (f) are present either dissolved or as solidparticulates in the milling mixture. Bead-milling has been found to workvery well for preparing the present composition. The Examples of thepresent disclosure use an Eiger Minimill, which is a laboratory-scalehorizontal bead mill found capable of providing a particle sizedistribution (analyzed by Mastersizer 2000, Fraunhofer presentationmode, dilution with 2-propanol) having D10, D50 and D90 percentiles of1.0-2.0 μm, 3.0-6.0 μm, and 9.0-15.0 μm, respectively. (This mill is nowmarketed as an EMI Mini Series Mill by Engineered Mills, Inc.,Grayslake, Ill.) Similar particle size reduction can also be achieved ona larger scale by utilizing equipment such as, but not limited to,Dyno-mill horizontal bead mills (Willy A Bachofen AG) and related typesof low energy mills or high energy mills, for instance those availablefrom Netzsch (Netzsch-Feinmahltechnik GmbH) or Buhler (Buhler Group).

Although the present composition can be applied directly to undesiredvegetation to be controlled or to the growing medium thereof, generallythe composition is first diluted with water in a volume ratio of 1:50 to1:1000, more typically 1:100 to 1:600 of present composition to water.Dilution of the present composition with water using agitation providesa spray mixture comprising an aqueous dispersion of particles ofcomponents (a) and (b), and an emulsion of component (c) in the water.The spray mixture is then applied to undesired vegetation (e.g.,foliage) or to the growing medium (e.g., soil) of the undesiredvegetation. For optimal herbicidal efficacy, most typically the spraymixture is applied to the foliage of the undesired vegetation. Oneskilled in the art can readily determine the optimal amount of spraymixture to apply based on the active herbicides and their concentrationsin the composition, the dilution ratio of the composition in water, thenature and growth stage of the undesired vegetation, and environmentalconditions. Often the spray mixture is applied in an amount of 50 to1000 L/ha, more typically 100 to 600 L/ha. Without further elaboration,it is believed that one skilled in the art using the precedingdescription can utilize the present invention to its fullest extent. Thefollowing non-limiting Examples are illustrative of the invention.

Formulation Examples

The following examples describe preparation of compositions of thepresent invention as well as comparative compositions omitting thethifensulfuron-methyl stabilizer (i.e. component (b)). Technical grademetsulfuron-methyl, thifensulfuron-methyl and fluroxypyr-meptyl wereused to prepare the example compositions. The inert formulatingingredients are identified in Table 1.

TABLE 1 Identity of Inert Formulating Ingredients Used in the ExamplesCAS Manu- Registry Chemical Ingredient facturer No. Composition FunctionAGNIQUE BASF 68919-53-9 Distilled methylated Liquid ME 18 soybean oil(C₁₆- carrier SD-U C₁₈ fatty acid methyl ester) ATPLUS Croda 73468-21-0Non-ionic/ionic Emulsifier 300F surfactant blend ATLOX Croda 58128-22-6Polymerized Dispersant LP-1 fatty acids BENTONE Elementis 887329-06-8Organically Thickener 1000 modified mont- morillonite clay

In the present examples (i.e. Examples 1 and 2, and Comparative Examples1 and 2) all the ingredients were thoroughly mixed and then subjected tomilling in a Eiger Minimill (horizontal bead mill manufactured by EigerManufacturing Inc. (now Engineered Mills, Inc., Grayslake, Ill.); 50 mLchamber size with 80% loading of glass media, 0.8-1.0 mm in diameter)with the chamber cooled to about 6-10° C., using 3800 rpm agitator speedand recirculation mode for 20 minutes to provide the example formulatedcompositions.

Example 1

To a 400-mL plastic beaker equipped with an overhead stirrer was added aC₁₆-C₁₈ fatty acid methyl ester (AGNIQUE ME 18 SD-U, 155.04 g), anon-ionic/ionic emulsifier blend (ATPLUS 300F, 30.05 g), a polymericfatty acid dispersant (ATLOX LP-1, 6.01 g), metsulfuron-methyl (1.03 g),thifensulfuron-methyl (6.01 g) and an organically modified clay (BENTONE1000, 2.02 g). The stirred mixture was then milled using the EigerMinimill to provide the finished formulated composition as afree-flowing suspension.

Comparative Example 1

To a 400-mL plastic beaker equipped with an overhead stirrer was added aC₁₆-C₁₈ fatty acid methyl ester (AGNIQUE ME 18 SD-U, 161.03 g), anon-ionic/ionic emulsifier blend (ATPLUS 300F, 30.01 g), a polymericfatty acid dispersant (ATLOX LP-1, 6.01 g), metsulfuron-methyl (1.03 g)and an organically modified clay (BENTONE 1000, 2.11 g).

The stirred mixture was then milled using the Eiger Minimill to providethe finished formulated composition as a free-flowing suspension.

Example 2

To a 400-mL plastic beaker equipped with an overhead stirrer was added aC₁₆-C_(˜)fatty acid methyl ester (AGNIQUE ME 18 SD-U, 114.98 g), anon-ionic/ionic emulsifier blend (ATPLUS 300F, 30.17 g), a polymericfatty acid dispersant (ATLOX LP-1, 6.01 g), fluroxypyr-meptyl (40.28 g),metsulfuron-methyl (1.06 g), thifensulfuron-methyl (6.11 g) and anorganically modified clay (BENTONE 1000, 2.08 g). The stirred mixturewas then milled using the Eiger Minimill to provide the finishedformulated composition as a free-flowing suspension.

Comparative Example 2

To a 400-mL plastic beaker equipped with an overhead stirrer was added aC₁₆-C₁₈ fatty acid methyl ester (AGNIQUE ME 18 SD-U, 121.16 g), anon-ionic/ionic emulsifier blend (ATPLUS 300F, 30.06 g), a polymericfatty acid dispersant (ATLOX LP-1, 6.02 g), fluroxypyr-meptyl (40.03 g),metsulfuron-methyl (1.03 g) and an organically modified clay (BENTONE1000, 2.11 g). The stirred mixture was then milled using the EigerMinimill to provide the finished formulated composition as afree-flowing suspension.

The weight percentage amounts of the ingredients in the exampleformulated compositions are listed in Table 2.

TABLE 2 Ingredient Amounts Used in Example (Ex.) 1 and 2 and ComparativeExample (C. Ex.) 1 and 2* Ingredient Component Ex. 1 C. Ex. 1 Ex. 2 C.Ex. 2 Metsulfuron-methyl (a) 0.5 0.5 0.5 0.5 Thifensulfuron-methyl (b)3.0 0 3.0 0 AGNIQUE ME 18 SD-U (c) 77.5 80.5 57.5 60.5 ATPLUS 300F (d)15.0 15.0 15.0 15.0 Fluroxypyr-meptyl (e) 0 0 20.0 20.0 ATLOX LP-1 (f)3.0 3.0 3.0 3.0 BENTONE 1000 (f) 1.0 1.0 1.0 1.0 *Amounts are listed aswt/wt %.

When prepared, the compositions were analyzed by HPLC formetsulfuron-methyl and thifensulfuron-methyl content. The stability ofmetsulfuron-methyl and thifensulfuron-methyl in the compositionsprepared was then determined by aging samples in ovens at 40° C. for 4and 8 weeks. Storage at 40° C. at 8 weeks simulates two-year storage atambient temperature. Control samples were stored in a freezer at −6° C.Assays of the control samples at the various time points were comparableto the initial, as-made assays. At the end of the allotted times,samples were removed from the ovens and analyzed by HPLC formetsulfuron-methyl or thifensulfuron-methyl content. The relativechemical stability was calculated by dividing the assay of the oven-agedsample by that of the control sample analyzed on the same day. Chemicalstability results are listed in Table 3.

TABLE 3 Chemical Stability of Metsulfuron-methyl andThifensulfuron-methyl (% Relative Stability) During Aging ofCompositions of Example (Ex.) 1 and 2 and Comparative Example (C. Ex.) 1and 2 at 40° C. % Relative Stability Thifensulfuron-methyl TimeMetsulfuron-methyl C. period Ex. 1 C. Ex. 1 Ex. 2 C. Ex. 2 Ex. 1 C. Ex.1 Ex. 2 Ex. 2 4 weeks 92.3 75.5 89.1 75.0 98.5 — 99.2 — 8 weeks 88.750.0 80.4 47.4 98.9 — 97.0 —

As can be seen from the stability results for Comparative Examples 1 and2 in Table 3, in the absence of thifensulfuron-methyl (component (b) ofthe present invention), one-quarter of the metsulfuron-methyl wasdegraded at 4 weeks and one-half of the metsulfuron-methyl was degradedat 8 weeks in this test. However as shown for Examples 1 and 2, addingjust 3% of thifensulfuron-methyl as component (b) to the 0.5% ofmetsulfuron-methyl by weight of the composition surprisingly slowed thedecomposition of metsulfuron-methyl to a remarkable extent, such thatafter 8 weeks more than 80% of the metsulfuron-methyl remained. Besidesfunctioning as a stabilizer of the metsulfuron-methyl, thethifensulfuron-methyl component itself showed excellent stability.

What is claimed is:
 1. A single liquid-phase herbicide composition comprising by weight of the composition: (a) from 0.1 to 1% of metsulfuron-methyl; (b) from 1 to 20% of thifensulfuron-methyl; (c) from 30 to 93% of one or more methylated seed oils of soybean, rapeseed or coconut; and (d) from 5 to 25% of one or more surfactants having an emulsifier property.
 2. The composition of claim 1 wherein component (c) comprises methylated soybean oil.
 3. The composition of claim 1 wherein component (d) comprises at least one surfactant selected from alkylbenzenesulfonates, alkylnaphthalenesulfonates, ethoxylated triglycerides, ethoxylated tri-styryl phenols, ethoxylated aliphatic alcohols, ethoxylated sorbitan mono- and tri-esters, ethoxylated sorbitol hexa-esters and polyoxyethylene-polyoxypropylene block copolymers, including mixtures thereof.
 4. The composition of claim 3 wherein component (d) comprises at least one surfactant selected from anionic surfactants and at least one surfactant selected from nonionic surfactants.
 5. The composition of claim 1 further comprising (e) up to 40% of one or more biologically active agents other than metsulfuron-methyl and thifensulfuron-methyl.
 6. The composition of claim 5 wherein component (e) comprises one or more fluroxypyr esters.
 7. The composition of claim 5 wherein component (e) comprises one or more bromoxynil esters.
 8. The composition of claim 1 further comprising (f) up to 63% of one or more additional formulating agents.
 9. The composition of claim 8 wherein component (f) comprises one or more polymerized fatty acids.
 10. The composition of claim 8 wherein component (f) comprises one or more organically modified clays.
 11. A process for preparing the composition of claim 1, the process comprising milling components (a) and (b) together in a liquid carrier comprising components (c) and (d).
 12. The composition of claim 2 wherein component (d) comprises at least one surfactant selected from alkylbenzenesulfonates, alkylnaphthalenesulfonates, ethoxylated triglycerides, ethoxylated tri-styryl phenols, ethoxylated aliphatic alcohols, ethoxylated sorbitan mono- and tri-esters, ethoxylated sorbitol hexa-esters and polyoxyethylene-polyoxypropylene block copolymers, including mixtures thereof.
 13. The composition of claim 2 wherein component (d) comprises at least one surfactant selected from anionic surfactants and at least one surfactant selected from nonionic surfactants.
 14. The composition of claim 2 further comprising (e) up to 40% of one or more biologically active agents other than metsulfuron-methyl and thifensulfuron-methyl.
 15. The composition of claim 3 further comprising (e) up to 40% of one or more biologically active agents other than metsulfuron-methyl and thifensulfuron-methyl.
 16. The composition of claim 2 further comprising (f) up to 63% of one or more additional formulating agents.
 17. The composition of claim 3 further comprising (f) up to 63% of one or more additional formulating agents.
 18. The composition of claim 9 wherein component (f) comprises one or more organically modified clays. 